ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Effect of Local Chain Dynamics on a Bioinert Interface

View Author Information
† § Department of Applied Chemistry, Education Center for Global Leaders in Molecular Systems for Devices, and §International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, Fukuoka 819-0395, Japan
Neutron Science Laboratory, High Energy Accelerator Research Organization, Ibaraki 305-0801, Japan
Department of Biochemical Engineering, Yamagata University, Yamagata 992-8510, Japan
*E-mail: [email protected]. Fax: +81-92-802-2880. Tel: +81-92-802-2879.
*E-mail: [email protected]. Fax: +81-92-802-2880. Tel: +81-92-802-2878.
Cite this: Langmuir 2015, 31, 12, 3661–3667
Publication Date (Web):March 11, 2015
Copyright © 2015 American Chemical Society

    Article Views





    Other access options
    Supporting Info (1)»


    Abstract Image

    Although many kinds of synthetic polymers have been investigated to construct blood-compatible materials, only a few have achieved success. To establish molecular designs for blood-compatible polymers, the chain structure and dynamics at the water interface must be understood using solid evidence as the first bench mark. Here we show that polymer dynamics at the water interface impacts on structure of the interfacial water, resulting in a change in protein adsorption and of platelet adhesion. As a particular material, a blend composed of poly(2-methoxyethyl acrylate) (PMEA) and poly(methyl methacrylate) was used. PMEA was segregated to the water interface. While the local conformation of PMEA at the water interface was insensitive to its molecular weight, the local dynamics became faster with decreasing molecular weight, resulting in a disturbance of the network structure of waters at the interface. This leads to the extreme suppression of protein adsorption and platelet adhesion.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.


    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    Jump To

    Experimental procedures for polymer synthesis, film preparation, and NR measurements and additional data for NR analyses. This material is available free of charge via the Internet at

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 52 publications.

    1. Yasuyuki Miyoshi, Yoshitomo Nakata, Tooru Kitagawa, Hideto Matsuyama, Tomohisa Yoshioka, Keizo Nakagawa. Effect of Surface Modification of Polyamide-Based Reverse Osmosis Membranes by Glycerol Monoacrylate–Butyl Acrylate Copolymers on Antifouling. Industrial & Engineering Chemistry Research 2024, 63 (9) , 4124-4133.
    2. Jin-Hyeok Hong, Haruki Mokudai, Takashi Masaki, Hisao Matsuno, Keiji Tanaka. Water-Induced Crystal Transition and Accelerated Relaxation Process of Polyamide 4 Chains in Microfibers. Biomacromolecules 2022, 23 (8) , 3458-3468.
    3. Hidenobu Taneda, Norifumi L. Yamada, Fumiya Nemoto, Yasuhisa Minagawa, Hisao Matsuno, Keiji Tanaka. Modification of a Polymer Surface by Partial Swelling Using Nonsolvents. Langmuir 2021, 37 (51) , 14941-14949.
    4. Kento Kawabata, Masayasu Totani, Daisuke Kawaguchi, Hisao Matsuno, Keiji Tanaka. Two-Dimensional Cellular Patterning on a Polymer Film Based on Interfacial Stiffness. Langmuir 2021, 37 (51) , 14911-14919.
    5. Shu-Jia Li, Xinghua Shi. Tailoring Antifouling Properties of Nanocarriers via Entropic Collision of Polymer Grafting. ACS Nano 2021, 15 (3) , 5725-5734.
    6. Jin-Hyeok Hong, Masayasu Totani, Daisuke Kawaguchi, Hiroyasu Masunaga, Norifumi L. Yamada, Hisao Matsuno, Keiji Tanaka. Design of a Bioinert Interface Using an Amphiphilic Block Copolymer Containing a Bottlebrush Unit of Oligo(oxazoline). ACS Applied Bio Materials 2020, 3 (11) , 7363-7368.
    7. Toyoaki Hirata, Hidenobu Taneda, Kazuya Nishio, Manabu Inutsuka, Norifumi L. Yamada, Fumiya Nemoto, Yasuhisa Minagawa, Hisao Matsuno, Keiji Tanaka. A Facile Surface Functionalization Method for Polymers Using a Nonsolvent. ACS Applied Bio Materials 2020, 3 (4) , 2170-2176.
    8. Yukari Oda, Manabu Inutsuka, Ryo Awane, Masayasu Totani, Norifumi L. Yamada, Masayuki Haraguchi, Masaaki Ozawa, Hisao Matsuno, Keiji Tanaka. A Dynamic Interface Based on Segregation of an Amphiphilic Hyperbranched Polymer Containing Fluoroalkyl and Oligo(ethylene oxide) Moieties. Macromolecules 2020, 53 (7) , 2380-2387.
    9. Nozomi Itagaki, Daisuke Kawaguchi, Yukari Oda, Fumiya Nemoto, Norifumi L. Yamada, Tetsuo Yamaguchi, Keiji Tanaka. Surface Effect on Frictional Properties for Thin Hydrogel Films of Poly(vinyl ether). Macromolecules 2019, 52 (24) , 9632-9638.
    10. Hung K. Nguyen, Manabu Inutsuka, Daisuke Kawaguchi, Keiji Tanaka. Direct Observation of Conformational Relaxation of Polymer Chains at Surfaces. ACS Macro Letters 2018, 7 (10) , 1198-1202.
    11. Kanta Yanagi, Norifumi L. Yamada, Kazuaki Kato, Kohzo Ito, Hideaki Yokoyama. Polyrotaxane Brushes Dynamically Formed at a Water/Elastomer Interface. Langmuir 2018, 34 (18) , 5297-5302.
    12. Takuma Kureha and Daisuke Suzuki . Nanocomposite Microgels for the Selective Separation of Halogen Compounds from Aqueous Solution. Langmuir 2018, 34 (3) , 837-846.
    13. Hidenobu Taneda, Atsuomi Shundo, Hisao Matsuno, and Keiji Tanaka . Design of a Well-Defined Polyrotaxane Structure on a Glassy Polymer Surface. Langmuir 2018, 34 (2) , 709-714.
    14. Nozomi Itagaki, Yukari Oda, Toyoaki Hirata, Hung Kim Nguyen, Daisuke Kawaguchi, Hisao Matsuno, and Keiji Tanaka . Surface Characterization and Platelet Adhesion on Thin Hydrogel Films of Poly(vinyl ether). Langmuir 2017, 33 (50) , 14332-14339.
    15. Haiye Wang, Joshua Jasensky, Nathan W. Ulrich, Junjie Cheng, Hao Huang, Zhan Chen, and Chunju He . Capsaicin-Inspired Thiol–Ene Terpolymer Networks Designed for Antibiofouling Coatings. Langmuir 2017, 33 (47) , 13689-13698.
    16. Uvinduni I. Premadasa, Narendra M. Adhikari, Susil Baral, Ahmed M. Aboelenen, and Katherine Leslee Asetre Cimatu . Conformational Changes of Methacrylate-Based Monomers at the Air–Liquid Interface Due to Bulky Substituents. The Journal of Physical Chemistry C 2017, 121 (31) , 16888-16902.
    17. Xiaolin Lu, Chi Zhang, Nathan Ulrich, Minyu Xiao, Yong-Hao Ma, and Zhan Chen . Studying Polymer Surfaces and Interfaces with Sum Frequency Generation Vibrational Spectroscopy. Analytical Chemistry 2017, 89 (1) , 466-489.
    18. Stephanie C. Chan, Joon Hee Jang, and Katherine A. Cimatu . Orientational Analysis of Interfacial Molecular Groups of a 2-Methoxyethyl Methacrylate Monomer Using Femtosecond Sum Frequency Generation Spectroscopy. The Journal of Physical Chemistry C 2016, 120 (51) , 29358-29373.
    19. Wesley Beckner, Yi He, and Jim Pfaendtner . Chain Flexibility in Self-Assembled Monolayers Affects Protein Adsorption and Surface Hydration: A Molecular Dynamics Study. The Journal of Physical Chemistry B 2016, 120 (40) , 10423-10432.
    20. Xu Li, Bolin Li, Xiaodong Zhang, Chengcheng Li, Zhirui Guo, Dongshan Zhou, and Xiaolin Lu . Detecting Surface Hydration of Poly(2-hydroxyethyl methacrylate) in Solution in situ. Macromolecules 2016, 49 (8) , 3116-3125.
    21. Shingo Kobayashi, Masaru Tanaka. Design of biomaterials through direct ring-opening metathesis polymerisation of functionalised cyclic alkenes. Molecular Systems Design & Engineering 2023, 8 (8) , 960-991.
    22. Akira Mochizuki, Yuko Miwa, Chie Yahata, Haruyo Saito, Yoshiki Oda. Properties of hydrated poly(2-methoxyethyl acrylate) observed by 13 C-nuclear magnetic resonance spectroscopy. International Journal of Polymer Analysis and Characterization 2023, 28 (5) , 523-535.
    23. Siyuan Wang, Yanqi Chen, Zhaoting Ling, Jia Li, Jun Hu, Fuming He, Qianming Chen. The role of dendritic cells in the immunomodulation to implanted biomaterials. International Journal of Oral Science 2022, 14 (1)
    24. Shu-Jia Li, Xinghua Shi. Regulation of nano-biological interface adhesion through grafted polymers. Chinese Science Bulletin 2022, 67 (31) , 3633-3641.
    25. Katherine Leslee A. Cimatu, Tharushi D. Ambagaspitiya, Uvinduni I. Premadasa, Narendra M. Adhikari, Adelaide Kruse, Emily Robertson, Shanshan Guan, Lihan Rong, Rigoberto Advincula, Benjamin J. Bythell. Polymer-solvent interaction and conformational changes at a molecular level: Implication to solvent-assisted deformation and aggregation at the polymer surface. Journal of Colloid and Interface Science 2022, 616 , 221-233.
    26. Jie Jin, Rajani Bhat, Utkarsh Mangal, Ji-Young Seo, YouJin Min, Jaehun Yu, Dae-Eun Kim, Kenichi Kuroda, Jae-Sung Kwon, Sung-Hwan Choi. Molecular weight tuning optimizes poly(2-methoxyethyl acrylate) dispersion to enhance the aging resistance and anti-fouling behavior of denture base resin. Biomaterials Science 2022, 10 (9) , 2224-2236.
    27. Tomoya Ueda, Daiki Murakami, Masaru Tanaka. Effect of amount of hydrated water and mobility of hydrated poly( 2‐methoxyethyl acrylate) on denaturation of adsorbed fibrinogen. Journal of Polymer Science 2021, 59 (22) , 2763-2770.
    28. Jin-Hyeok Hong, Masayasu Totani, Takashi Yamamoto, Paul M. Dietrich, Andreas Thissen, Hisao Matsuno, Keiji Tanaka. Near-ambient pressure X-ray photoelectron spectroscopy for a bioinert polymer film at a water interface. Polymer Journal 2021, 53 (8) , 907-912.
    29. Akira Mochizuki, Yoshiki Oda, Yuko Miwa. Comparative study on water structures of poly(tetrahydrofurfuryl acrylate) and poly(2-hydroxyethyl methacrylate) by nuclear magnetic resonance spectroscopy. Journal of Biomaterials Science, Polymer Edition 2021, 26 , 1-16.
    30. Jin-Hyeok Hong, Masayasu Totani, Daisuke Kawaguchi, Norifumi L. Yamada, Hisao Matsuno, Keiji Tanaka. Poly[oligo(2-ethyl-2-oxazoline) methacrylate] as a surface modifier for bioinertness. Polymer Journal 2021, 53 (5) , 643-653.
    31. Masaru Tanaka, Shigeaki Morita, Tomohiro Hayashi. Role of interfacial water in determining the interactions of proteins and cells with hydrated materials. Colloids and Surfaces B: Biointerfaces 2021, 198 , 111449.
    32. Akira Mochizuki, Yuko Miwa, Chie Yahata, Dai Ono, Yoshinobu Oda, Tsubasa Kawaguchi. Water structure of poly(2-methoxyethyl acrylate) observed by nuclear magnetic resonance spectroscopy. Journal of Biomaterials Science, Polymer Edition 2020, 31 (8) , 1024-1040.
    33. Matthew Penna, Irene Yarovsky. Nanoscale in silico classification of ligand functionalised surfaces for protein adsorption resistance. Nanoscale 2020, 12 (13) , 7240-7255.
    34. Masaru Tanaka, Shingo Kobayashi, Daiki Murakami, Fumihiro Aratsu, Aki Kashiwazaki, Takashi Hoshiba, Kazuki Fukushima. Design of Polymeric Biomaterials: The “Intermediate Water Concept”. Bulletin of the Chemical Society of Japan 2019, 92 (12) , 2043-2057.
    35. Yukari Oda. Construction of hydrophilic surfaces with poly(vinyl ether)s and their interfacial properties in water. Polymer Journal 2019, 51 (10) , 955-962.
    36. Hisao MATSUNO, Keiji TANAKA. Aggregation State and Thermal Molecular Motion of a Bio-Inert Polymer at the Water Interface. KOBUNSHI RONBUNSHU 2019, 76 (3) , 185-195.
    37. Sho Kishinaka, Akihiro Morita, Tatsuya Ishiyama. Molecular structure and vibrational spectra at water/poly(2-methoxyethylacrylate) and water/poly(methyl methacrylate) interfaces: A molecular dynamics simulation study. The Journal of Chemical Physics 2019, 150 (4)
    38. Masaru Tanaka. Design of Multifunctional Soft Biomaterials: Based on the Intermediate Water Concept. 2019, 423-432.
    39. Yukari ODA. Adhesion Control of Biogenic Components ontoPolymers Based on Interfacial Designs. Journal of The Adhesion Society of Japan 2018, 54 (2) , 44-49.
    40. Hisao Matsuno, Ryota Tsukamoto, Yukari Oda, Keiji Tanaka. Platelet adhesion on the surface of a simple poly(vinyl ether). Polymer 2017, 116 , 479-486.
    41. Toyoaki Hirata, Hisao Matsuno, Daisuke Kawaguchi, Manabu Inutsuka, Tomoyasu Hirai, Masaru Tanaka, Keiji Tanaka. Dynamics of a bioinert polymer in hydrated states by dielectric relaxation spectroscopy. Physical Chemistry Chemical Physics 2017, 19 (2) , 1389-1394.
    42. Narendra M. Adhikari, Uvinduni I. Premadasa, Katherine L. A. Cimatu. Sum frequency generation vibrational spectroscopy of methacrylate-based functional monomers at the hydrophilic solid–liquid interface. Physical Chemistry Chemical Physics 2017, 19 (32) , 21818-21828.
    43. Hisao Matsuno, Ryota Tsukamoto, Yu Kaneshiro, Satoru Yamada, Keiji Tanaka. Platelet Adhesion on Films of Poly(vinylene carbonate) and Its Derivatives. Chemistry Letters 2016, 45 (8) , 913-915.
    44. Yukari Oda, Cui Zhang, Daisuke Kawaguchi, Hisao Matsuno, Shokyoku Kanaoka, Sadahito Aoshima, Keiji Tanaka. Design of Blood‐Compatible Interfaces with Poly(vinyl ether)s. Advanced Materials Interfaces 2016, 3 (12)
    45. Hisao Matsuno, Ryota Tsukamoto, Shinichiro Shimomura, Tomoyasu Hirai, Yukari Oda, Keiji Tanaka. Platelet-adhesion behavior synchronized with surface rearrangement in a film of poly(methyl methacrylate) terminated with elemental blocks. Polymer Journal 2016, 48 (4) , 413-419.
    46. Yuji Higaki, Motoyasu Kobayashi, Daiki Murakami, Atsushi Takahara. Anti-fouling behavior of polymer brush immobilized surfaces. Polymer Journal 2016, 48 (4) , 325-331.
    47. Kshitij Jha, Emmanuel Anim-Danso, Selemon Bekele, George Eason, Mesfin Tsige. On Modulating Interfacial Structure towards Improved Anti-Icing Performance. Coatings 2016, 6 (1) , 3.
    48. Settimio Pacelli, Vijayan Manoharan, Anna Desalvo, Nikita Lomis, Kartikeya Singh Jodha, Satya Prakash, Arghya Paul. Tailoring biomaterial surface properties to modulate host-implant interactions: implication in cardiovascular and bone therapy. Journal of Materials Chemistry B 2016, 4 (9) , 1586-1599.
    49. Toyoaki Hirata, Hisao Matsuno, Daisuke Kawaguchi, Norifumi L. Yamada, Masaru Tanaka, Keiji Tanaka. Construction of a blood-compatible interface based on surface segregation in a polymer blend. Polymer 2015, 78 , 219-224.
    50. T. Hirata, H. Matsuno, D. Kawaguchi, N. L. Yamada, M. Tanaka, K. Tanaka. Effect of interfacial structure on bioinert properties of poly(2-methoxyethyl acrylate)/poly(methyl methacrylate) blend films in water. Physical Chemistry Chemical Physics 2015, 17 (26) , 17399-17405.
    51. Ilaria Solano, Pietro Parisse, Federico Gramazio, Ornella Cavalleri, Gianangelo Bracco, Matteo Castronovo, Loredana Casalis, Maurizio Canepa. Spectroscopic ellipsometry meets AFM nanolithography: about hydration of bio-inert oligo(ethylene glycol)-terminated self assembled monolayers on gold. Physical Chemistry Chemical Physics 2015, 17 (43) , 28774-28781.
    52. Masaru TANAKA. Design of Biocompatible Polymers Based on the Intermediate Water Concept. Journal of The Adhesion Society of Japan 2015, 51 (9) , 423-433.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect